Herbicidal pyridine compounds

ABSTRACT

The novel compounds of formula I:                    
     wherein R, A, X 1 , X 2 , X 3 , Z and m have the meaning given in claim 1, and the agronomically acceptable salts or N-oxides thereof, and herbicidal compositions containing such compounds as active ingredients.

This application is a division of Ser. No. 09/287,898 filed Apr. 17,1999, U.S. Pat. No. 6,130,188 which claims benefit of No. 60/084,282 May5, 1998 under 119e.

BACKGROUND OF THE INVENTION

Selective herbicidal compounds play an important role in agriculture andrelated fields. Growers seek herbicides that kill pest plants, but donot reduce crop yield. Although numerous selective herbicides have beendescribed, there is nevertheless a considerable interest in newcompounds having a superior or different activities, because the knownherbicidal compounds either are not suitable for application in certaincrops, or are not sufficiently selective.

Selective herbicides the active ingredients of which are pyridinederivatives, and particularly 2,6-substituted pyridines, are known fromWO 94/22833.

The European patent application EP 0 109 751 discloses herbicidal6-difluormethoxy- and 6-tetrafluorethoxy-2-phenyloxypyridines.

However, 2,6-disubstituted pyridine derivatives in which ahaloalkylmethoxy or a haloalkenyloxy group is attached to the pyridinegroup in the 2-position have not yet been described.

SUMMARY OF THE INVENTION

The present invention provides novel compounds of the general formula(I)

wherein

one of the groups X¹, X² and X³ represents N or CR¹ and the othersrepresent CR¹;

R¹ each independently represent a hydrogen or halogen atom or anoptionally substituted alkyl, alkenyl, alkinyl, alkoxy, alkoxyalkyl,alkoxyalkoxy, group or a haloalkyl, haloalkoxy, cyano, nitro or SF₅group; or —S(O)_(p)—R¹, in which p is 0, 1 or 2, and R¹ represents analkyl or haloalkyl group; or —NR²R³, in which R² and R³ eachindependently represent a hydrogen atom, an alkyl, alkenyl, aralkyl oraryl group, or R⁴O—CY—, in which R⁴ represents an alkyl group, and Yrepresents O or S;

A represents an optionally substituted aryl group, an optionallysubstituted 5- or 6-membered nitrogen-containing heteroaromatic group oran optionally substituted thienyl group;

R represents an optionally substituted haloalkyl or haloalkenyl group;

m is 0, 1, 2 or 3;

Z represents an oxygen or sulfur atom,

and the agronomically acceptable salts or N-oxides thereof;

with the proviso that R represents an optionally substituted haloalkenylgroup, in the event that m is 0.

The new compounds show an excellent selective herbicidal activity invarious crops.

It is an object of the present invention to provide novel, selectiveherbicidal compounds.

It is also an object of the invention to provide methods for controllingundesired plant growth by contacting said plants with a herbicidallyeffective amount of the new compounds.

It is another object of the invention to provide selective herbicidalcompositions containing the new compounds as active ingredients.

These and other objects and features of the invention will be moreapparent from the detailed description set forth hereinbelow, and fromthe appended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

It has surprisingly been found that the compounds of the general formula(I)

wherein

A, R, m, X¹ through X³ and Z are as described above and theagronomically acceptable salts or N-oxides thereof, show considerableherbicidal activity and high selectivity in certain crops, such as maizeand rice, in pre- and post-emergence applications on both broadleaf andgrassy weed species.

In the definitions of the new compounds, an aryl group is suitably anoptionally substituted phenyl or naphthyl group. Within the definitionof A, the 5- or 6-membered nitrogen-containing heteroaryl groupscomprise optionally substituted 5- or 6-membered heterocycles containingone or more nitrogen and/or oxygen and/or sulphur atoms, 1 to 3 nitrogenatoms being preferred. Examples of such groups are pyrazolyl,imidazolyl, triazolyl, tetrazolyl, pyridyl, pyrazinyl, pyrimidyl,pyridazinyl, isoxazolyl, isothiazolyl and triazinyl groups. A alsoincludes optionally substituted thienyl groups.

Generally, in compounds of the present invention, alkyl, alkenyl oralkynyl groups, unless otherwise specified, may be linear or branchedand may contain up to 12, preferably up to 6, and most preferably up to4, carbon atoms. Examples of such groups are methyl, ethyl, propyl,vinyl, allyl, propargyl, isopropyl, butyl, isobutyl and tertiary-butylgroups. The alkyl portion of a haloalkyl, haloalkenyl, haloalkoxy,alkylthio, haloalkylthio or alkoxy group suitably has up to 12 carbonatoms, preferably up to 6, and most preferably up to 4, carbon atoms.The double bond of the alkenyl and haloalkenyl groups is as a rulelocated in the 1- or 2-position with respect to the point of theirattachment. The number of carbon atoms in the alkoxyalkyl, alkoxyalkoxyor dialkoxyalkyl groups is up to 6, preferably up to 4, e.g.methoxymethyl, methoxymethoxy, methoxyethyl, ethoxymethyl, ethoxyethoxy,dimethoxymethyl.

“Halogen” means a fluorine, chlorine, bromine or iodine atom, preferablyfluorine, chlorine or bromine.

m is preferably 1 or 2.

Haloalkyl, haloalkenyl, haloalkylthio and haloalkoxy are preferablymono-, di-, tri-, tetra- or pentafluoroalkyl, -alkenyl, -alkylthio and-alkoxy, or monochloro- or dichloroalkenyl, or monobromoalkenyl,especially preferred are trifluoromethyl, tetrafluoroethyl,pentafluoroethyl, octafluorobutyl, 3,3,3-trifluoroprop-1-enyl,2-methyl-3,3,3-trifluoroprop-1-enyl, 4,4,4-trifluorobut-1-enyl,1,2-difluorobuta-1,3-dienyl, 1- or 2-chlorovinyl, 2,2-dichlorovinyl,1,2-dichlorovinyl, 1,2-dichloroprop-1-enyl, 3,3,3-trichloroprop-1-enyl,2-bromoallyl, difluoromethoxy, trifluoromethylthio, difluoromethylthioand trifluoromethoxy.

When any groups are designated as being optionally substituted, thesubstituent groups which are optionally present may be any of thosecustomarily employed in the modification and/or development ofpesticidal compounds and are especially substituents that maintain orenhance the herbicidal activity associated with the compounds of thepresent invention, or influence persistence of action, soil or plantpenetration, or any other desirable property of such herbicidalcompounds.

There may be one or more of the same or different substituents presentin each part of the molecules. In relation to moieties defined above ascomprising an optionally substituted alkyl group, including alkyl partsof haloalkyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, alkylaminoand dialkylamino groups, specific examples of such substituents includephenyl, halogen atoms, nitro, cyano, hydroxyl, C₁₋₄-alkoxy,C₁₋₄-haloalkoxy, C₁₋₄-haloalkylthio and C₁₋₄-alkoxycarbonyl groups.

In relation to moieties defined above as comprising an optionallysubstituted aryl or heteroaryl group, optional substituents includehalogen, nitro, cyano, amino, hydroxyl, C₁₋₄-alkyl, C₁₋₄-alkoxy,C₁₋₄-haloalkyl, C₁₋₄-haloalkylthio, C₁₋₄-haloalkoxy, C₂₋₄haloalkenyl,and halosulfanyl groups having 1-5 halogen atoms, such as SF₅. From 1 to5 substituents may be present, 1 to 2 substituents being preferred.Typically, haloalkyl, haloalkenyl, haloalkoxy and haloalkylthio groupsare trifluoromethyl, difluoromethoxy, trifluoromethoxy,difluoromethylthio and trifluoromethylthio groups.

Preferred compounds within the above definitions are those in which Arepresents a phenyl, pyridyl or pyrazolyl group, unsubstituted orsubstituted by one or more identical or different substituents selectedfrom halogen atoms, alkyl, alkoxy, haloalkyl, haloalkylthio, haloalkoxyand pentahalosulfanyl groups. Preferably, at least one substituent isattached in the 3-position with respect to the carbon atom attached tothe group Z. Most preferred A is a group of formula A,

in which

R⁸ represents a halogen atom, or an alkyl, alkoxy, haloalkyl,haloalkylthio, haloalkoxy or pentahalosulfanyl group;

V represents CH or NCH₃;

W represents N, S, N—CH or CH—CH.

X¹ and X³ preferably represent CH or C-Halogen, in particular C—F, andX² represents CR¹, in which R¹ has the meaning given and is preferablyalkyl or alkoxy.

Preferred embodiments of the present invention are:

(a) A compound of formula I, wherein Z represents an oxygen atom.

(b) A compound of formula I, wherein R represents a group of formula 1:

(c) in which

R⁵ through R⁷ represent a hydrogen or halogen atom or an optionallysubstituted alkyl or alkoxy group; at least one of which being a halogenatom, a haloalkyl or haloalkoxy group; in particular a fluoro, chloro orbromo atom or a C₁₋₃ haloalkyl group, and B¹ and B² each independentlyrepresent a hydrogen or halogen atom or taken together a double bond, inparticular wherein R represents a haloalkyl or haloalkenyl groupselected from trifluoromethyl, tetrafluoroethyl, pentafluoroethyl,octafluorobutyl, 3,3,3-trifluoroprop-1-enyl,2-methyl-3,3,3-trifluoroprop-1-enyl, 4,4,4-trifluorobut-1-enyl,1,2-difluorobuta-1,3-dienyl, 1- or 2-chlorovinyl, 2,2-dichlorovinyl,1,2-dichlorovinyl, 1,2-dichloroprop-1-enyl, 3,3,3-trichloroprop-1-enyland 2-bromoallyl.

The double bond of the haloalkenyl group has preferably the(E)-configuration.

(d) A compound of formula I, wherein A represents a group selected fromoptionally substituted phenyl, pyridyl, thienyl and pyrazolyl,preferably wherein A represents a group selected from the formulae (2),(3), (4), and (5):

 wherein

R⁸ each independently represents a halogen atom or an optionallysubstituted alkyl group;

R⁹ represents an alkyl group; and

n represents an integer of 1 to 5, in particular wherein A representsone of the groups 2″, 3″, 4″ or 5″:

 where R⁸ is a chlorine atom, a trifluoromethyl or a difluoromethoxygroup.

(e) A compound of formula IA

 wherein R¹, R⁵, R⁶, R⁷, R⁸, B¹, B² and Z have the meaning given above;

L represents a hydrogen or fluorine atom;

W—V represents N—CH, S—CH, N—CH—CH, CH—CH—CH or N—NCH₃;

(f) A compound according to claim 1selected from the group consisting of2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-6-(2,2,3,3-tetrafluoropropyloxy)4-methylpyridine;2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-6-(4,4,4-trifluorobut-2-enyloxy)-4-methylpyridine;2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-6-(3-bromobut-3-enyloxy)-4-methylpyridine;2-(5-trifluoromethylthien-3-yloxy)-6-(2,2,3,3-tetrafluoropropyloxy)-4-methylpyridine;2-(5-trifluoromethylthien-3-yloxy)-6-(4,4,4-trifluorobut-2-enyloxy)-4-methylpyridine;2-(3-trifluoromethylphenyloxy)-6-(2,2,3,3-tetrafluoropropyloxy)-4-methylpyridine;2-(3-trifluoromethylphenyloxy)-6-(4,4,4-trifluorobut-2-enyloxy)-4-methylpyridine;2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-6-(4,4,4-trifluorobut-1-enyloxy)-4-methylpyridine;2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-6-(3-chloroprop-2-enyloxy)-4-methylpyridine;2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-6-(2,2,3,3-tetrafluoropropyloxy)-4-methoxypyridine;4-cyano-6-(4,4,4-trifluorobut-2-enyloxy)-2-(5-trifluoromethylthienyl-3-oxy)pyridine;4-cyano-6-(3,3-dichloroprop-2-enyloxy)-2-(5-trifluoromethylthienyl-3-oxy)pyridine;4-cyano-6-(3-chlorobut-2-enyloxy)-2-(5-trifluoromethylthienyl-3-oxy)pyridine;6-(3-chlorobut-2-enyloxy)-2-(3-trifluoromethylphenyloxy)-4-methylpyridine;2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-6-(3-methyl-4,4,4-trifluorobutyloxy)-4-methylpyridine;2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-6-(2-methyl-4,4,4-trifluorobutyloxy)-4-methylpyridine;6-(3,3-dichloroprop-2-enyloxy)-3,5-difluoro-2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methylpyridine;3,5-difluoro-6-(3-chloroprop-2-enyloxy)-2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methylpyridine;3,5-difluoro-6-(3-chlorobut-2-enyloxy)-2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methylpyridine;6-(2-chloroprop-2-enyloxy)-2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methylpyridine;6-(4-chlorobut-2-enyloxy)-2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methylpyridine;2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methyl-6-(3,4,4-trifluorobut-3-enyloxy)-pyridine;and6-(4,4-difluoro-3-methylbut-3-enyloxy)-2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methylpyridine.

The compounds of this invention can be prepared according to thefollowing methods:

Method (A): reacting a respective compound of the general formula II,

in which X¹, X², X³ and A have the meaning given, with a compound ofgeneral formula III,

HO—(CH₂)_(m)—R  (III)

in which R and m have the meaning given, or a metal salt thereof.

Method (B): Alternatively, a compound of formula IV,

in which A and X¹ through X³ are as defined above, is reacted with acompound of formula III in the presence of a dehydrating agent,preferably in the presence of triphenylphosphine and diethylazodicarboxylate (Mitsonobu method).

Method (C): Alternatively, a compound of formula IV,

in which A and X¹ through X³ are as defined above, is reacted with acompound of formula V,

LG—(CH₂)_(m)—R  (V)

in which LG represents a suitable leaving group, such as a halogen atomor a tosylate or mesylate group, in the presence of a base.

Method (D): Alternatively, a compound of formula VI,

in which R, m and X¹ through X³ are as defined above, and LG denotes asuitable leaving group, is reacted with a compound of formula VII,

A—OH  (VII)

in which A has the meaning given, in the presence of a base.

The N-oxides of the compounds of formula I can be prepared according toknown methods, particularly with the aid of the following methods:

Method (E): A compound of formula VIII,

in which A and X¹ through X³ are as defined above and Hal is a halogenatom, is reacted with a compound of formula III in the presence of abase. The compounds of formula VIII can be prepared by reaction of2,6-dihalopyridine N-oxide with a compound of formula VII in thepresence of a base.

These reactions are conveniently carried out in an organic solvent atelevated temperature. Generally, any polar organic solvent is suitable,e.g. dimethylformamide, tetrahydrofuran, sulfolane, pyridines. The metalsalts of the compounds of formula III are suitably alkali metal salts,preferably the sodium or potassium salts. In some cases, the presence ofcopper salts has been found to be useful.

The metal salts are conveniently generated by reaction of the compoundof formula III with a suitable metal base, a metal carbonate or hydride.

The prepared compounds of formula I may be isolated and purified usingconventional methods and techniques.

The starting compounds for the preparation of compounds of thisinvention are either known from WO 94/22833 or can be prepared accordingto known methods.

The following acids are suitable for the preparation of theagronomically acceptable salts of the compounds of formula I:hydrohalides like hydrochloric or hydrobromic acid, phosphoric acid,nitric acid, sulfuric acid, mono- or bifunctional carboxylic acids andhydroxycarboxylic acids like acetic acid, maleic acid, succinic acid,fumaric acid, citric acid, salicylic acid, sorbic acid or lactic acidand sulfonic acids like p-toluenesulfonic acid ornaphthalene-1,5-diyl-disulfonic acid. The agronomically acceptable saltsof the compounds of formula I are prepared according to conventionalsalt formation procedures, for example by dilution of a compound offormula I in a suitable organic solvent, addition of an acid andisolation of the salt formed by, for example, filtration and optionalpurification by washing with an inert solvent.

The compounds of general formula I have been found to have herbicidalactivity. Accordingly, the invention further provides a herbicidalcomposition which comprises an active ingredient, which includes atleast one compound of formula I as defined above, and one or morecarriers. A method of making such a composition is also provided whichcomprises bringing a compound of formula I as defined above intoassociation with the carrier(s). Such a composition may contain a singleactive ingredient or a mixture of several active ingredients of thepresent invention. It is also envisaged that different isomers ormixtures of isomers may have different levels or spectra of activity andthus compositions may comprise individual isomers or mixtures ofisomers.

A composition according to the invention preferably contains from 0.5%to 95% by weight (w/w) of active ingredient.

A carrier in a composition according to the invention is any materialwith which the active ingredient is formulated to facilitate applicationto the locus to be treated, which may be, for example, a plant, seed orsoil, or to facilitate storage, transport or handling. A carrier may bea solid or a liquid, including material which is normally a gas butwhich has been compressed to form a liquid.

The compositions may be manufactured into e.g. emulsion concentrates,solutions, oil in water emulsions, wettable powders, soluble powders,suspension concentrates, dusts, granules, water dispersible granules,micro-capsules, gels and other formulation types by well-establishedprocedures. These procedures include intensive mixing and/or milling ofthe active ingredients with other substances, such as fillers, solvents,solid carriers, surface active compounds (surfactants), and optionallysolid and/or liquid auxilaries and/or adjuvants. The form of applicationsuch as spraying, atomizing, dispersing or pouring may be chosen likethe compositions according to the desired objectives and the givencircumstances.

Solvents may be aromatic hydrocarbons, e.g. Solvesso® 200, substitutednaphthalenes, phthalic acid esters, such as dibutyl or dioctylphthalate, aliphatic hydrocarbons, e.g. cyclohexane or paraffins,alcohols and glycols as well as their ethers and esters, e.g. ethanol,ethyleneglycol mono- and dimethyl ether, ketones such as cyclohexanone,strongly polar solvents such as N-methyl-2-pyrrolidone, orγ-butyrolactone, higher alkyl pyrrolidones, e.g. n-octylpyrrolidone orcyclohexylpyrrolidone, epoxidized plant oil esters, e.g. methylatedcoconut or soybean oil ester and water. Mixtures of different liquidsare often suitable.

Solid carriers, which may be used for dusts, wettable powders, waterdispersible granules, or granules, may be mineral fillers, such ascalcite, talc, kaolin, montmorillonite or attapulgite. The physicalproperties may be improved by addition of highly dispersed silica gel orpolymers. Carriers for granules may be porous material, e.g. pumice,kaolin, sepiolite, bentonite; non-sorptive carriers may be calcite orsand. Additionally, a multitude of pre-granulated inorganic or organicmaterials may be used, such as dolomite or crushed plant residues.

Pesticidal compositions are often formulated and transported in aconcentrated form which is subsequently diluted by the user beforeapplication. The presence of small amounts of a carrier which is asurfactant facilitates this process of dilution. Thus, preferably atleast one carrier in a composition according to the invention is asurfactant. For example, the composition may contain at two or morecarriers, at least one of which is a surfactant.

Surfactants may be nonionic, anionic, cationic or zwitterionicsubstances with good dispersing, emulsifying and wetting propertiesdepending on the nature of the compound according to general formula Ito be formulated. Surfactants may also mean mixtures of individualsurfactants.

The compositions of the invention may for example be formulated aswettable powders, water dispersible granules, dusts, granules,solutions, emulsifiable concentrates, emulsions, suspension concentratesand aerosols. Wettable powders usually contain 5 to 90% w/w of activeingredient and usually contain in addition to solid inert carrier, 3 to10% w/w of dispersing and wetting agents and, where necessary, 0 to 10%w/w of stabilizer(s) and/or other additives such as penetrants orstickers. Dusts are usually formulated as a dust concentrate having asimilar composition to that of a wettable powder but without adispersant, and may be diluted in the field with further solid carrierto give a composition usually containing 0.5 to 10% w/w of activeingredient. Water dispersible granules and granules are usually preparedto have a size between 0.15 mm and 2.0 mm and may be manufactured by avariety of techniques. Generally, these types of granules will contain0.5 to 90% w/w active ingredient and 0 to 20% w/w of additives such asstabilizer, surfactants, slow release modifiers and binding agents. Theso-called “dry flowables” consist of relatively small granules having arelatively high concentration of active ingredient. Emulsifiableconcentrates usually contain, in addition to a solvent or a mixture ofsolvents, 1 to 80% w/v active ingredient, 2 to 20% w/v emulsifiers and 0to 20% w/v of other additives such as stabilizers, penetrants andcorrosion inhibitors. Suspension concentrates are usually milled so asto obtain a stable, non-sedimenting flowable product and usually contain5 to 75% w/v active ingredient, 0.5 to 15% w/v of dispersing agents, 0.1to 10% w/v of suspending agents such as protective colloids andthixotropic agents, 0 to 10% w/v of other additives such as defoamers,corrosion inhibitors, stabilizers, penetrants and stickers, and water oran organic liquid in which the active ingredient is substantiallyinsoluble; certain organic solids or inorganic salts may be presentdissolved in the formulation to assist in preventing sedimentation andcrystalization or as antifreeze agents for water.

Aqueous dispersions and emulsions, for example compositions obtained bydiluting the formulated product according to the invention with water,also lie within the scope of the invention.

Of particular interest in enhancing the duration of the protectiveactivity of the compounds of this invention is the use of a carrierwhich will provide slow release of the pesticidal compounds into theenvironment of a plant which is to be protected.

The biological activity of the active ingredient can also be increasedby including an adjuvant in the spray dilution. An adjuvant is definedhere as a substance which can increase the biological activity of anactive ingredient but is not itself significantly biologically active.The adjuvant can either be included in the formulation as a coformulantor carrier, or can be added to the spray tank together with theformulation containing the active ingredient.

As a commodity the compositions may preferably be in a concentrated formwhereas the end user generally employs diluted compositions. Thecompositions may be diluted to a concentration down to 0.001% of activeingredient. The doses usually are in the range from 0.01 to 10 kga.i./ha.

Examples of formulations according to the invention are:

Emulsion Concentrate (EC) Active Ingredient Compound of Example 11 30%(w/v) Emulsifier(s) e.g. Atlox ® 4856 B and 5% (w/v) Atlox ® 4858 B¹⁾Solvent e.g. Shellsol ® A²⁾ to 1000 ml Suspension Concentrate (SC)Active Ingredient Compound of Example 11 50% (w/v) Dispersing agent e.g.Soprophor ® FL³⁾ 3% (w/v) Antifoaming agent e.g. Rhodorsil ® 422³⁾ 0.2%(w/v) Structure agent e.g. Kelzan ® S⁴⁾ 0.2% (w/v) Antifreezing agente.g. Propylene glycol 5% (w/v) Biocidal agent e.g. Proxel ®⁵⁾ 0.1% (w/v)Water to 1000 ml Wettable Powder (WP) Active Ingredient Compound ofExample 11 60% (w/w) Wetting agent e.g. Atlox ® 4995¹⁾ 2% (w/w)Dispersing agent e.g. Witcosperse ® D-60⁶⁾ 3% (w/w) Carrier/Filler e.g.Kaolin 35% (w/w) Water Dispersible Granules Active Ingredient Compoundof Example 11 50% (w/w) Dispersing/Binding agent e.g. Witcosperse ®D-450⁶⁾ 8% (w/w) Wetting agent e.g. Morwet ® EFW⁶⁾ 2% (w/w) Antifoamingagent e.g. Rhodorsil ® EP 6703³⁾ 1% (w/w) Disintegrant e.g. Agrimer ®ATF⁷⁾ 2% (w/w) Carrier/Filler e.g. Kaolin 35% (w/w) ¹⁾Productcommercially available from ICI Surfactants ²⁾Product commerciallyavailable from Deutsche Shell AG ³⁾Product commercially available fromRhône-Poulenc ⁴⁾Product commercially available from Kelco Co. ⁵⁾Productcommercially available from Zeneca ⁶⁾Product commercially available fromWitco ⁷⁾Product commercially available from International SpecialityProducts

The chemical composition of the trademark ingredients is shown below:

rimer ® ATF ss-linked homopolymer of N-vinyl-2-pyrrolidone ox ® 4856 B/ture containing calcium alkyl aryl sulfonate, fatty Atlox ® 4858 B¹alcohol ethoxylates and light aromatics/mixture containing calcium alkylaryl sulfonate, fatty alcohol ethoxylates and light aromatics ox ® 4995yoxyethylene alkyl ether Kelzan ® S nthan gum rwet ® EFW aldehydecondensation product pylene glycol xel ® eous dipropylene glycolsolution containing 20% 1,2-benisothiazolin-3-one Rhodorsil ® 422 ionicaqueous emulsion of polydimethylsiloxanes odorsil ® EP 6703 apsulatedsilicone ellsol ® A ture of C₉-C₁₀ aromatic hydrocarbons prophor ® FLyoxyethylene polyaryl phenyl ether phosphate amine salt cosperse ® D-450ture of sodium salts of condensed naphthalene sulfonic acid and alkylsulfonates cosperse ® D-60 ture of sodium salts of condensed naphthalenesulfonic acid and alkylarylpolyoxy acetates

The compositions of this invention can also comprise other compoundshaving biological activity, e.g. compounds having similar orcomplementary pesticidal activity or compounds having plant growthregulating, fungicidal/herbicidal or insecticidal activity. Thesemixtures of pesticides can have a broader spectrum of activity than thecompound of general formula I alone. Furthermore, the other pesticidecan have a synergistic effect on the pesticidal activity of the compoundof general formula I.

The active ingredients according to the invention can be employed aloneor as formulations in combination with conventional herbicides. Suchcombinations of at least two herbicides can be included in theformulation or also added in a suitable form with the preparation of thetank mix. For such mixtures at least one of the following knownherbicides can be used:

ametrydione, metabenzthiazuron, metamitron, metribuzin, 2,4-D, 2,4-DB,2,4-DP, alachlor, alloxydim, asulam, atrazin, bensulfuron, bentazon,bifenox, bromoxynil, butachlor, chloridazon, chlorimuron, chlorpropham,chlorsulfuron, chlortoluron, cinmethylin, clopyralid, cyanazin,cycloate, cycloxydim, dichlobenil, diclofop, eptame, ethiozin,fenoxaprop, fluazifop, fluometuron, fluridone, fluroxypyr, fomesafen,glyphosate, haloxyfop, hexazinone, imazamethabenz, imazapyr, imazaquin,imazethapyr, ioxynil, isoproturon, lactofen, MCPA, MCPP, mefenacet,metazachlor, metolachlor, metsulfuron, molinate, norflurazon, oryzalin,oxyfluorfen, pendimethalin, picloram, pretilachlor, propachior,pyridate, quizalofopethyl, sethoxydim, simetryne, terbutryne,thiobencarb, triallate, trifluralin, diflufenican, propanil, triclopyr,dicamba, desmedipham, acetochlor, fluoroglycofen, halosafen,tralkoxydim, amidosulfuron, cinosulfuron, nicosulfuron, pyrazosulfuron,thiameturon, thifensulfuron, triasulfuron, oxasulfuron, azimsulfuron,tribenuron, esprocarb, prosulfocarb, terbutylazin, benfuresate,clomazone, di-methazone, dithiopyr, isoxaben, quinchlorac, qinmerac,sulfosate, cyclosulfamuron, imazamox, imazamethapyr, flamprop-M-methyl,flamprop-M-isopropyl, picolinafen, thiafluamide, isoxaflutole,flurtamone, daimuron, bromobutide, methyldimron, dimethenamid,sulcotrione, sulfentrazone, oxadiargyl, acifluorfen, cafenstrole,carfentrazone, diuron, glufosinate.

Mixtures with other active ingredients like fungicides, insecticides,acaricides, and nematicides are possible.

For a more clear understanding of the invention, specific examples areset forth below. These examples are merely illustrations and are not tobe understood as limiting the scope and underlying principles of theinvention in any way. Various modifications of the invention in additionto those shown and described herein will become apparent to thoseskilled in the art from the following examples and foregoingdescription. Such modifications are also intended to fall within thescope of the appended claims.

EXAMPLE 1

(a)6-Hydroxy-2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methylpyridine

Method A

A mixture of2,6-bis(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methylpyridine(prepared according to WO 94/22833; 4.2 g, 10 mmol) and NaOH (1 g, 25mmol) is heated in DMSO (50 ml) and water (5 ml) for 36 h at 100° C.After cooling, the reaction mixture is diluted with water and acidifiedwith hydrochloric acid. The mixture is diluted with pentane/ethylacetate (300 ml by volume ration 1/1) and the organic layer is washed 6times with water. The organic layer is dried with anhydrous magnesiumsulfate, filtered and evaporated in vacuo. Purification by flashchromatography (silica gel: pentane/ethyl acetate 8/2 v/v and 7/3 v/v)yields the title compound (1.9 g, 70% yield) of m.p. 159° C.

Method B

A mixture of6-benzyloxy-2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methylpyridine(prepared according to WO94/22833; 34 g, 93 mmol) and catalytic amountsof palladium on carbon is reduced in methanol by hydrogen at ambienttemperature. After filtration, the solution is evaporated in vacuo.Treatment of the residue with a mixture of pentane and diisopropyl etheryields the title compound (18.9 g, 74% yield) of m.p. 159° C.

(b)(E)-2-(1-Methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methyl-6-(4,4,4-trifluorobut-2-envloxy)pyridine

A mixture of6-hydroxy-2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methylpyridine(0.8 g, 2.93 mmol), 4,4,4-trifluorobut-2-en-1-ol (0.44 g, 3.5 mmol),triphenylphosphine (0.92 g, 3.51 mmol) and diethyl azodicarboxylate(0.61 g, 3.51 mmol) in dry dioxane (3 ml) is stirred for 1.5 h atambient temperature. The reaction mixture is diluted with pentane/ethylacetate (by volume ration 1/1) and filtered through a bed of silica gel.The filtrate is washed with water. The organic layer is dried withanhydrous magnesium sulfate, filtered and evaporated in vacuo.Purification by flash chromatography (silica gel: pentane/ethyl acetate9/1 v/v) yields the title compound (1.11 g, 70% yield) as an colorlessoil.

EXAMPLE 2

2-(1-Methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methyl-6-(4,4,4-trifluorobut-1-enyloxy)pyridine

To a solution of trimethylsulfoxonium iodide (4.5 g, 20.5 mmol) in DMSO(50 ml) is added NaH (60% in oil, 0.82 g, 20.5 mmol) and the resultingmixture is stirred for 1 h at ambient temperature. To the resultingsolution is added dropwise a solution of(E)-2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methyl-6-(4,4,4-trifluorobut-2-enyloxy)pyridine(example 1, 7.1 g, 18.6 mmol) at 10° C. After 3 h of stirring at ambienttemperature, the dark mixture is hydrolyzed with water (200 ml) andextracted 3 times with diethylether (50 ml). The organic fractions arewashed with water, dried over anhydrous magnesium sulfate, filtered andevaporated in vacuo. Purification by flash chromatography (silica gel:pentane/ethyl acetate 9/1 v/v) yields the title compound (0.22 g, 3.1%yield) of m.p. 56° C.

EXAMPLE 3

(E)-2-(1-Methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methyl-6-(3-chloroprop-2-enyloxy)pyridine

A mixture of6-hydroxy-2-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methylpyridine(0.9 g, 3.3 mmol) and NaH (60% in oil, 0.16 g, 4 mmol) in acetonitrile(20 ml) and DMF (1 ml) is stirred for 10 min at ambient temperature and(E)-1,3-dichloropropene (0.4 g, 3.6 mmol) is added. After stirring for60 h at ambient temperature, the remaining NaH is deactivated and theresulting mixture is diluted with pentane/ethyl acetate (by volumeration 1/1) and filtered through a bed of silica gel. The filtrate iswashed with water. The organic layer is dried with anhydrous magnesiumsulfate, filtered and evaporated in vacuo. Purification by flashchromatography (silica gel: pentane/ethyl acetate 9/1 v/v) yields thetitle compound (0.6 g, 52% yield) as an colorless oil.

EXAMPLE 4

(a) 2,4,6-Tris(1-methyl-3-trifluoromethylpyrazol-5-yloxy)pyridine

A mixture of 4.8 g (36 mmol) 2,4,6-trifluoropyridine, 19.8 g (119 mmol)5-hydroxy-1-methyl-3-trifluoromethylpyrazole and 18.1 g (131 mmol)potassium carbonate in 25 ml anhydrous sulfolane is stirred and heatedto 80° C. over a period of 3 days. After cooling, the mixture is dilutedwith pentane/ethyl acetate (by volume ration 1/1) and filtered through abed of silica gel. The filtrate is washed 10 times with water and theorganic layer is dried over magnesium sulfate. After removal of thesolvents, the residue is washed with isopropyl ether and 19.1 g (93%yield) colorless crystals of melting point 130° C. are obtained.

(b) 2,6-Bis(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methoxypyridine

A 3 ml aliquot of a 25% solution of potassium methylate (10 mmol) in drymethanol is added to a solution of 5.7 g (10 mmol)2,4,6-tris-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)pyridine in 20 mlanhydrous methanol. After 2 hours at ambient temperature, the reactionmixture is heated to reflux. The solvent is removed under reducedpressure and ethyl acetate is added to the residue. The mixture iswashed with a 2 N sodium hydroxide solution. After drying and filtrationof the organic layer, the solvents are removed and the residue is washedwith diisopropyl ether and pentane. Colorless crystals (1.9 g, 43%yield) of melting point 107° C. are obtained.

(c)2-(1-Methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methoxy-6-(2,2,3,3-tetrafluoropropyloxly)pyridine

To a mixture of 2,2,3,3-tetrafluoropropan-1-ol (0.29 g, 2.2 mmol) in drysulfolane (2 ml) is added NaH (60% in oil, 0.09 g, 2.2 mmol) and2,6-bis-(1-methyl-3-trifluoromethylpyrazol-5-yloxy)-4-methoxypyridine(0.8 g, 1.8 mmol). After stirring at 110° C. for 3.7 h the mixture iscooled to ambient temperature. The resulting mixture is diluted withpentane/ethyl acetate (by volume ration 1/1) and filtered through a bedof silica gel. The filtrate is washed 10 times with water. The organiclayer is dried with anhydrous magnesium sulfate, filtered and evaporatedin vacuo. Purification by flash chromatography (silica gel:pentane/ethyl acetate 9/1 v/v) yields the title compound (0.72 g, 57%yield) of m.p. 73-74° C.

EXAMPLE 5

(a) 3-Hydroxy-5-trifluoromethylthiophene

Method A

5A Ethyl 3-methoxy-3-trifluoromethylacrylate

Cesium carbonate (132.8 g) was added to a mixture of ethyl4,4,4-trifluoroacetoacetate (75.0 g) and dimethylformamide (400 ml). Thereaction mixture was heated to 20° C. for 30 minutes. A mixture ofmethyl tosylate (83.4 g) and dimethylformamide (150 ml) was added to theresulting reaction mixture within 40 minutes. The mixture was heated for3 hours and cooled to room temperature. Upon dilution with water (800ml) the reaction mixture was extracted with diethyl ether three times.The combined organic phases were washed with water and dried. Themixture was concentrated and the residue distilled under reducedpressure to yield the product as a clear liquid (48.5 g, 60%) with aboiling point of 62-70° C. at 12 mm.

5B Methyl (3-hydroxy-5-trifluoromethylthien-2-yl)-carboxylate

A solution of 1M potassium hydroxide in methanol (30 ml) is added to acooled mixture of 5A (4.6 g), methyl thioglycolate (2.46 g) and methanol(10 ml). The resulting reaction mixture was stirred for 24 hours at roomtemperature. Then the mixture was poured on ice and acidified with 6Nsulfuric acid (pH=2). The mixture is extracted with diethyl ether twice.The combined organic phases were washed with water and dried. Themixture was concentrated and the residue is distilled under reducedpressure to yield the product as a clear liquid (3.4 g, 65%) with aboiling point of 42-45° C. at 0.10 mm.

5C (3-Hydroxy-5-trifluoromethylthien-2-yl)-carboxylic Acid

A mixture of 5B (2.38 g) and methanol (20 ml) was added to a stirredsolution of sodium hydroxide (1.68 g) in water (20 ml). The reactionmixture was heated at reflux for 3 hours. The reaction mixture wascooled to room temperature and concentrated in vacuo. The concentratewas cooled to 5° C. and acidified with concentrated HCl (3.5 ml). Theresulting suspension was stirred at 5° C. for 30 minutes. The solid wascollected by filtration, washed with water, then dried in vacuo at35-40° C. to give the free acid (1.45 g, 65%).

5D 3-Hydroxy-5-trifluoromethylthiophen

5C (1.80 g) was slowly heated under argon. Evolution of gas was observedat 90° C. Heating was continued for additional 3.5 hours at 90° C. Theresulting oil was distilled under reduced pressure (boiling point 70-74°C. at 4 mm) to yield 1.18 g (82%) of compound 5D.

Method B

5E Methyl (3-benzyloxy-5-trifluoromethylthien-2-yl)-carboxylate

A mixture of 5B (5.0 g) and dimethylformamide (50 ml) is treated withsodium hydride (1.06 g). Benzylbromide (3.15 ml) was slowly added to theresulting reaction mixture and stirred at room temperature for 20 hours.The reaction mixture was poured into water. The mixture was extractedwith diethyl ether twice. The combined organic phases were washed withwater, dried and concentrated in vacuo. The crude product waschromatographed (hexane/dichloromethane, 1/1) to give the product as awhite solid (4.5 g, 64%) with a melting point of 52-53.5° C.

5F (3-Benzyloxy-5-trifluoromethylthien-2-yl)-carboxylic Acid

A mixture of 5E (3.80 g) and tetrahydrofuran (12 ml) was heated toreflux in 2N sodium hydroxide (12 ml) for 12 hours. Then the mixture waspoured on ice and acidified with 6N sulfuric acid (pH=1-2). The mixtureis extracted with diethyl ether twice. The combined organic phases werewashed with water and dried. The mixture was concentrated and theresidue is distilled under reduced pressure to yield the product as awhite solid (3.22 g, 89%) with a melting point of 142-144° C.

5G 3-Benzyloxy-5-trifluoromethylthiophen

A mixture of 5F (14.5 g) and quinoline (50 ml) was treated with copperpowder (4.57 g) and heated to 150° C. The reaction mixture is heated for25 minutes at 150° C. and cooled to room temperature. The mixture wasfiltered and washed with water. Aqueous quinoline was acidified with 6NHCl (pH=2) and extracted with diethyl ether twice. The combined organicphases were washed with water and dried. The mixture was concentratedand the residue was chromatographed to yield a yellow liquid (8.74 g,71%).

5D 3-Hydroxy-5-trifluoromethylthiophen

A mixture of 5G (7.75 g) and tetrachloromethane (50 ml) was treated withiodotrimethylsilane (12.30 ml) and heated to 60° C. for 12 hours. Thereaction mixture was stirred at room temperature for 12 hours. Water (50ml) was added and the resulting reaction mixture was extracted withdichloromethane three times. The combined organic phases were washedwith water and dried. The crude reaction mixture was eluted throughhexane (100 g/silica gel) to remove benzyliodide and then with diethylether. The etheral phases were concentrated and distilled in vacuo togive the product (3.33 g, 74%) having a boiling point of 65-66° C. at 4mm.

(b) 4-Cyano-2,6-bis(5-trifluoromethylthienyl-3-oxy)pyridine

A mixture of 5D (14.6 g, 86.7 mmol) and NaH (60% in oil, 3.47 g, 86.7mmol) in dry sulfolane is stirred at 30° C. 2,6-Dichloro-4-cyanopyridine(5 g, 29 mmol) is added and the resulting mixture is heated to 90° C.for 1.75 h. After cooling, the reaction mixture is diluted withpentane/ethyl acetate (by volume ration 1/1) and washed 10 times withwater and once with 1 N NaOH. The organic layer is dried with anhydrousmagnesium sulfate, filtered and evaporated in vacuo. Purification byflash chromatography (silica gel: pentane/ethyl acetate 95/5 v/v) yieldsthe title compound (8 g, 64% yield) of m.p. 103-104° C.

(c)4-Cyano-2-(5-trifluoromethlthienyl-3-oxy)-6-(2-methylbenzyloxy)pyridine

A mixture of 2-methylbenzylalcohol (0.79 g, 6.3 mmol) and NaH (60% inoil, 0.1 g, 6.3 mmol) in dry sulfolane (7 ml) is stirred for 30 min at50° C. After adding of4-cyano-2,6-bis(5-trifluoromethylthienyl-3-oxy)pyridine (2.5 g, 5.73mmol), the mixture is heated for 7 h at 90° C. Further 0.1 equivalentsof NaH and 2-methylbenzylalcohol are added and the reaction mixture isstirred for 3 h at 90° C. After cooling to ambient temperature, thereaction mixture is diluted with pentane/ethyl acetate (by volume ration1/1) and washed 10 times with water. The organic layer is dried withanhydrous magnesium sulfate, filtered and evaporated in vacuo.Purification by flash chromatography (silica gel: pentane/ethyl acetate95/5 v/v) yields the title compound (0.89 g, 44% yield) of m.p. 78° C.

(d) 4-Cyano-6-hydroxy-2-(5-trifluoromethylthienyl-3-oxy)-pyridine

To a solution of4-cyano-2-(5-trifluoromethylthienyl-3-oxy)-6-(2-methylbenzyloxy)pyridine(0.52 g, 1.33 mmol) in dichloromethane (10 ml) is addediodotrimethylsilane (0.246 ml, 1.73 mmol) at 0° C. under nitrogen. After4 days at 0° C. the mixture is stirred for 5 h at ambient temperature.The reaction mixture is diluted with pentane/ethyl acetate (by volumeration 1/1) and washed with water and with 2 N hydrochloric acid. Theorganic layer is dried with anhydrous magnesium sulfate, filtered andevaporated in vacuo. Purification by flash chromatography (silica gel:pentane/ethyl acetate 9/1 v/v) yields the title compound (0.24 g, 63%yield) of m.p. 192° C.

(e)(E)-4-Cyano-6-(4,4,4-trifluorobut-2-enyloxy)-2-(5-trifluoromethylthienyl-3-oxy)pyridine

To a mixture of4-cyano-6-hydroxy-2-(5-trifluoromethylthienyl-3-oxy)pyridine (0.19 g,0.66 mmol), 4,4,4-trifluorobut-2-en-1-ol (0.082 ml, 0.79 mmol),triphenylphosphine (0.21 g, 0.79 mmol) in dry THF (5 ml) is addeddiethyl azodicarboxylate (0.125 ml, 0.79 mmol) and the mixture isstirred for 7 h at ambient temperature. The reaction mixture is dilutedwith pentane/ethyl acetate (by volume ration 1/1) and washed with 2 Nhydrochloric acid, with 2 N NaOH and with concentrated sodiumbicarbonate. The organic layer is dried with anhydrous magnesiumsulfate, filtered and evaporated in vacuo. Purification by flashchromatography (silica gel: pentane/ethyl acetate 95/5 v/v) yields thetitle compound (0.25 g, 58% yield) of m.p. 60° C.

EXAMPLES 6-39

The compounds listed in TABLE 1 can be prepared by methods analogeous tothose described in examples 1 to 5, and according to the methodsdescribed in the foregoing description.

TABLE 1 Compounds of formula Ia (Ia)

m.p. Example A Y¹ Y² R¹ R [° C.]  6 1-CH₃-3-CF₃-pyrazol-5-yl H H CH₃—CF₂CF₂H 71  7 1-CH₃-3-CF₃-pyrazol-5-yl H H CH₃ —C₂F₅ 53  81-CH₃-3-CF₃-pyrazol-5-yl H H CH₃ —(CF₂)₃—CF₂H oil  91-CH₃-3-CF₃-pyrazol-5-yl H H CH₃ —CH₂—CBr═ CH₂ oil 10 3-CF₃-phenyl H HCH₃ —CH═ CH—CF₃ oil 11 1-CH₃-3-CF₃-pyrazol-5-yl H H CH₃ —CH═ CCl—CH₃ 6112 1-CH₃-3-CF₃-pyrazol-5-yl H H CH₃ —CH═ CCl₂ 47 131-CH₃-3-CF₃-pyrazol-5-yl H H CH₃ —CCl═ CHCl, (E) oil 141-CH₃-3-CF₃-pyrazol-5-yl H H CH₃ —CCl═ CHCl, (Z) oil 151-CH₃-3-CF₃-pyrazol-5-yl H H CH₃ —CH═ CHCl oil 161-CH₃-3-CF₃-pyrazol-5-yl H H CH₃ —CCl═ CCl—CH₃ oil 171-CH₃-3-CF₃-pyrazol-5-yl H H CH₃ —CH═ CH—CCl₃ oil 18 3-CF₃-phenyl H HCH₃ —CF₂CF₂H 19 3-CF₃-phenyl H H CH₃ —C₂F₅ 20 3-CF₃-phenyl H H CH₃—(CF₂)₃—CF₂H 21 3-CF₃-phenyl H H CH₃ —CH═ CCl—CH₃ 22 3-CF₃-phenyl H HCH₃ —CH═ CCl₂ 23 5-CF₃-thien-3-yl H H CN —CF₂CF₂H 24 5-CF₃-thien-3-yl HH CN —C₂F₅ 25 5-CF₃-thien-3-yl H H CN —(CF₂)₃—CF₂H 26 5-CF₃-thien-3-yl HH CN —CH═ CCl—CH₃ 27 5-CF₃-thien-3-yl H H CN —CH═ CCl₂ oil 285-CF₃-thien-3-yl H H CN —CH═ CClCH₃ oil 29 5-CF₃-thien-3-yl H H CN—CH═CHCF₃ 60 30 3-CF₃-phenyl H H CH₃ —CH═CClCH₃ oil 311-CH₃-3-CF₃-pyrazol-5-yl H H CH₃ —C(CH₃)═ CHCF₃ oil 321-CH₃-3-CF₃-pyrazol-5-yl H H CH₃ —CH═C(CH₃)CF₃ oil 331-CH₃-3-CF₃-pyrazol-5-yl F F CH₃ —CH═ CCl₂ 44 341-CH₃-3-CF₃-pyrazol-5-yl F F CH₃ —CH═CHCl 73 35 1-CH₃-3-CF₃-pyrazol-5-ylF F CH₃ —CH═CClCH₃ 66 36 1-CH₃-3-CF₃-pyrazol-5-yl H H CH₃ —CCl═CH₂ 59 371-CH₃-3-CF₃-pyrazol-5-yl H H CH₃ —CH═CH—CH₂Cl oil 381-CH₃-3-CF₃-pyrazol-5-yl H H CH₃ —CH₂CF═CF₂ 39 1 CH₃-3-CF₃-pyrazol-5-ylH H CH₃ CH₂C(CH₃)═CF₂

Herbicidal Activity Tests

1. Pre-emergence Herbicidal Evaluation of Test Compounds

The pre-emergence herbicidal activity of the compounds of the presentinvention is exemplified by the following test in which the seeds of avariety of monocotyledonous and dicotyledonous plants are seperatelymixed with potting soil and planted on top of approximately one inch ofsoil in separate pots. After planting, the pots are sprayed with theselected aqueous acetone solution containing test compound in sufficientquantity to provide the equivalent of about 0.0125 to 0.4 kg per hectareof test compound per pot. The treated pots are then placed on greenhousebenches, watered and cared for in accordance with conventionalgreenhouse procedures. From 2 to 4 weeks after treatment, the tests areterminated and each pot is examined and rated according to the ratingsystem set forth below.

% Difference in Growth Rating System Versus Untreated Control 0-Noeffect 0 1-Trace effect 1-5 2-Slight effect  6-15 3-Moderate effect16-29 4-Injury 30-44 5-Definite injury 45-64 6-Herbicidal effect 65-797-Good herbicidal effect 80-90 8-Approaching complete kill 91-999-Complete kill 100

Plant Species Used GLXMA Glycine max soyabeans HORVW Hordeum vulgarewinter barley ORYSA Oryza sativum rice TRZAW Triticum aestivum winterwheat ZEAMX Zea mays maize ABUTH Abutilon theophrasti velvetleaf AMBELAmbrosia artemiisifolia ragweed CASOB Cassia obtusifolia sicklepod GALAPGalium aparine cleaver IPOHE Ipomoea hederacea morning glory LAMPULamium purpureum purple deadnettle MATIN Matricaria inodora mayweedSOLNI Solanum nigrum black nightshade STEME Stellaria media chickweedALOMY Alopecurus myosuroides black grass DIGSA Digitaria sanguinalislarge crabgrass ECHCG Echinochloa grus galli barnyard grass SETVISetaria viridis green foxtail

The herbicidal proficiency of the active ingredients of the presentinvention is evident from the test results which are recorded in Table Abelow.

Crop Selectivity and Weed Control of Compounds According to theInvention in Pre-emergence Application

The compounds of the invention showed good selectivity in maize up tothe highest dose of 0.4 kg/ha. Furthermore, the compounds of the presentinvention displayed good selectivity in soybeans. At crop selectivedoses the compounds of the present invention showed superior weedcontrol. The results of these tests are presented in Table A below.

TABLE A Crop selectivity and weed control of compounds according to theinvention in pre-emergence application-crop and weed species G H O T Z AA C G I L M S S A D E S L O R R E B M A A P A A O T L I C E X R Y Z A UB S L O M T L E O G H T Dose M V S A M T E O A H P I N M M S C V Example(kg/ha) A W A W X H L B P E U N I E Y A G I 1 0.4 5 5 5 4 5 9 9 9 9 9 99 9 9 9 9 9 1 0.1 4 5 4 3 8 9 9 7 7 9 9 9 9 8 7 9 1 0.025 1 2 2 1 2 7 99 2 5 9 9 8 9 6 5 9 1 0.013 1 1 2 1 1 7 5 0 1 2 8 8 4 5 4 3 9 2 0.4 4 53 3 4 9 9 9 9 7 9 9 9 9 9 9 9 2 0.1 3 2 1 2 6 8 9 2 3 9 8 8 9 7 8 9 20.025 1 0 1 0 1 4 3 1 0 3 8 6 1 0 1 2 6 2 0.013 0 0 0 0 0 1 1 0 0 1 8 40 0 1 0 5 4 0.4 8 4 3 4 5 9 9 9 8 9 9 9 8 9 8 8 9 4 0.1 6 3 2 1 3 7 9 75 9 9 9 8 9 8 8 9 4 0.025 4 2 1 0 1 5 9 4 3 6 8 8 8 6 3 5 8 4 0.013 1 11 0 1 3 4 3 1 3 8 8 6 4 3 5 6 0.4 5 3 2 2 5 9 9 9 8 8 9 9 9 9 9 9 9 9 60.1 3 2 1 1 3 3 9 5 2 9 9 8 9 9 9 8 8 6 0.025 2 0 0 0 1 2 1 1 1 7 4 3 23 6 6 0.013 0 0 0 0 0 1 1 1 0 7 4 1 1 0 4 7 0.4 3 3 2 2 2 7 9 2 5 9 9 98 9 8 7 8 7 0.1 2 2 1 1 0 1 6 1 2 8 8 4 7 4 6 4 5 7 0.025 0 0 1 0 0 0 10 1 6 3 1 5 1 1 1 2 7 0.013 0 0 0 0 0 0 0 0 0 0 0 2 8 0.4 4 4 1 3 2 9 88 9 9 9 8 9 8 9 8 9 8 0.1 2 3 1 1 1 7 8 6 9 9 9 8 9 7 9 6 9 8 0.025 1 10 0 1 1 7 1 2 8 8 3 4 1 2 1 3 8 0.013 0 0 0 0 1 0 5 1 2 8 8 1 1 1 1 1 111 0.4 4 6 3 4 5 9 9 8 9 9 9 9 9 9 9 9 9 11 0.1 2 3 2 2 3 9 9 6 8 8 9 89 9 9 8 9 11 0.025 1 3 1 2 2 7 9 3 4 8 9 7 9 9 8 6 8 11 0.013 0 3 1 0 13 7 1 2 5 9 5 8 6 8 4 7 12 0.4 4 8 3 6 5 9 9 9 9 9 9 8 9 9 9 9 9 12 0.13 5 1 3 3 8 9 8 9 9 9 8 9 9 9 8 9 12 0.025 2 4 0 2 2 7 8 4 3 9 9 8 8 8 95 9 12 0.013 1 3 0 1 0 2 8 1 2 8 8 5 6 3 9 3 5 28 0.4 3 1 8 1 8 9 8 9 99 28 0.1 1 0 7 0 8 9 8 9 8 9 28 0.025 0 0 5 0 5 9 4 9 3 3 35 0.12 3 9 99 9 35 0.06 3 9 9 9 9 35 0.04 1 9 8 9 8 36 0.04 5 2 8 8 9 9 9 9 9 9 9 360.1 3 2 5 3 3 8 9 9 8 9 9 36 0.025 2 0 5 0 2 7 7 5 4 8 9

The compounds of the invention were quite selective in soybeans (seeTable A), particularly for the compounds of Examples 7 and 11.Furthermore, the compounds of the invention, as demonstrated by Examples7 and 8, exhibited good selectivity in maize. Overall, the compounds ofthe invention displayed excellent weed control. Examples 1 and 11 showsuperior activity against Setaria, Abutilon and Stellaria.

2. Post-emergence Herbicidal Evaluation of Test Compounds

The post-emergence herbicidal activity of the compounds of the presentinvention is demonstrated by the following test, wherein a variety ofmonocotyledonous and dicotyledonous plants are treated with formulationsprepared from solutions of the test compounds in acetone containing 0.4%by weight of an alkylphenol/ethylene oxide condensate available underthe trade mark TRITON X-155. These acetone solutions are diluted withwater and the resulting formulations applied at dosage levels equivalentof about 0.03 to 0.4 kg per hectare of test compound per pot. Afterspraying the plants are placed on greenhouse benches and are cared forin the usual manner, commensurate with conventional greenhousepractices. From 2 to 4 weeks after treatment, the seedling plants areexamined and rated according to the rating system provided above. Arating 0 indicates growth as untreated control, a rating 9 indicatesdeath. The results of the test are set out in Table B below.

TABLE B Crop selectivity and weed control of compounds according to theinvention in post-emergence application G H O T Z A A C G I L M S S A DE S L O R R E B M A A P A A O T L I C E X R Y Z A U B S L O M T L E O GH T Dose M V S A M T E O A H P I N M M S C V Example (kg/ha) A W A W X HL B P E U N I E Y A G I 1 0.4 8 5 5 5 6 8 7 5 8 9 8 8 5 6 8 8 8 8 1 0.018 5 3 3 5 8 7 5 8 9 8 8 5 5 8 8 8 8 1 0.03 6 3 2 2 2 8 6 5 7 9 8 8 5 5 67 5 5 2 0.4 8 3 3 3 5 9 8 9 9 8 9 8 8 8 9 7 8 2 0.1 8 3 3 3 4 8 6 7 9 88 8 6 5 9 5 8 2 0.03 7 3 2 2 2 8 5 5 8 8 6 7 4 2 7 2 4 4 0.4 8 5 4 5 5 67 9 9 8 7 5 8 8 8 9 9 4 0.1 8 3 2 3 3 6 6 9 9 7 5 6 6 7 8 8 4 0.03 5 3 22 2 4 3 6 8 7 5 4 6 3 5 6 6 6 0.4 7 3 1 3 5 6 6 6 7 9 7 6 4 3 8 7 6 60.25 7 1 1 1 1 2 3 4 3 7 4 4 1 2 2 4 2 6 0.1 7 2 1 2 2 4 4 6 8 6 6 2 2 66 3 7 0.4 3 3 3 3 2 5 5 9 6 8 0 5 5 9 7 8 7 0.1 3 3 2 2 2 5 9 2 7 0 5 49 7 4 7 0.03 2 3 2 2 2 1 3 3 0 2 0 2 2 2 4 2 8 0.4 8 3 2 3 3 7 8 7 8 9 99 8 8 8 9 8 8 8 0.1 7 3 2 2 1 5 8 7 7 9 8 9 5 5 7 9 5 6 8 0.03 5 2 1 2 11 5 2 5 7 8 9 3 3 2 8 2 3 11 0.4 4 4 3 5 8 8 9 9 8 8 8 8 8 9 8 8 11 0.14 3 3 5 7 7 9 9 3 8 6 6 8 9 8 6 11 0.03 3 1 3 2 5 3 6 6 0 7 3 4 6 9 8 512 0.4 8 6 4 5 6 9 7 8 9 9 8 8 8 8 9 9 9 9 12 0.1 8 5 3 3 4 9 6 8 8 9 88 8 8 9 9 9 9 12 0.03 5 3 2 3 2 8 5 8 7 9 8 8 8 8 8 8 9 9

In post-emergence application the compounds of the invention are veryselective in maize up to 25 g/ha, displaying good overall levels ofperformance against weeds (Table B). In barley the compounds of theinvention, in particular Examples 6, 7 and 8, are effective for bothgrass control such as Setaria virides and broad-leaved weed control atcrop selective doses.

What is claimed is:
 1. A compound of the general formula (I)

wherein X¹, X² and X³ represent CR¹; R¹ each independently represent ahydrogen or halogen atom or an unsubstituted or substituted alkyl,alkenyl, alkynyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, group or ahaloalkyl, haloalkoxy, cyano, nitro or SF₅ group; or —S(O)_(p)—R⁰, inwhich p is 0, 1 or 2, and R⁰ represents an alkyl or haloalkyl group; or—NR²R³, in which R² and R³ each independently represent a hydrogen atom,an alkyl, alkenyl, aralkyl or aryl group, or R⁴O—CY—, in which R⁴represents an alkyl group, and Y represents O or S; A represents anunsubstituted or substituted thienyl group; R represents an optionallysubstituted haloalkyl or haloalkenyl group; m is 0, 1, 2 or 3; Zrepresents an oxygen or sulfur atom; and the agronomically acceptablesalts or N-oxides thereof; with the proviso that R represents anunsubstituted or substituted haloalkenyl group, in the event that m is0.
 2. A compound as claimed in claim 1, wherein Z represents an oxygenatom.
 3. A compound as claimed in claim 1, wherein R represents a groupof formula 1:

in which R⁵ through R⁷ represent a hydrogen or halogen atom or anunsubstituted or substituted alkyl or alkoxy group; at least one ofwhich being a halogen atom, a haloalkyl or haloalkoxy group; and B¹ andB² each independently represent a hydrogen or halogen atom or takentogether a double bond.
 4. A compound as claimed in claim 1, wherein Arepresents

and R⁸ represents a halogen atom or an unsubstituted or substitutedalkyl group.
 5. A compound of formula IA

wherein R¹ represents a hydrogen or halogen atom or an unsubstituted orsubstituted alkyl, alkenyl, alkynyl, alkoxy, alkoxyalkyl, alkoxyalkoxy,group or a haloalkyl, haloalkoxy, cyano, nitro or SF₅ group; or—S(O)_(p)R⁰, in which p is 0, 1 or 2, and R⁰ represents an alkyl orhaloalkyl group; or —NR²R³, in which R² and R³ each independentlyrepresent a hydrogen atom, an alkyl, alkenyl, aralkyl or aryl group, orR⁴O—CY—, in which R⁴ represents an alkyl group, and Y represents O or S:R⁵ through R⁷ represent a hydrogen or halogen atom or an unsubstitutedor substituted alkyl or alkoxy group; at least one of which being ahalogen atom, a haloalkyl or haloalkoxy group; B¹ and B² eachindependently represent a hydrogen or halogen atom or taken together adouble bond; Z represents an oxygen or sulfur atom; Y represents ahydrogen or fluorine atom; and W—V represents S—CH.
 6. A compoundaccording to claim 1 selected from the group consisting of2-(5-trifluoromethylthien-3-yloxy)-6-(2,2,3,3-tetrafluoropropyloxy)-4-methylpyridine;2-(5-trifluoromethylthien-3-yloxy)-6-(4,4,4-trifluorobut-2-enyloxy)-4-methylpyrdine;4-cyano-6-(4,4,4-trifluorobut-2-enyloxy)-2-(5-trifluoromethylthienyl-3-oxy)pyridine;4-cyano-6-(3,3-dichloroprop-2-enyloxy)-2-(5-trifuoromrnethylthienyl-3-oxy)pyridine;4-cyano-6-(3-chlorobut-2-enyloxy)-2-(5-trifluoromethylthienyl-3-oxy)pyridine.7. A herbicidal composition comprising at least one compound of generalformula I, as claimed in claim 1, together with a carrier.
 8. Acomposition as claimed in claim 7, comprising at least two carriers, atleast one of which is a surface-active agent.
 9. A method of combatingundesired plant growth at a locus, comprising application to the locusof a compound of general formula I, as claimed in claim 1 or of acomposition as claimed in claim 7.